Polycyclic compounds such as steroidal compounds have a wide variety of uses, for example, as pharmaceutical agents. In steroidal compounds that contain enone moieties, it is sometimes desirable to stereoselectively reduce the C—C double bond to preferentially produce either the β-reduced or the α-reduced compound. In either event, it is useful to reduce the C—C double bond stereoselectively in order to obviate complex chromatographic purifications.